Plastic and plastic composition and process of making same.



UNITED STATES PATENT OFFICE. v

I I JACOB S. ROBESON, OF.AU' SABLE FORKS, NEW YORK.

' PLASTIC AND PLASTIC COMPOSITION AND PROCESS OF MAKING Specificationof Letters Patent.

Patented'Ju1y29, 19 13.

No Drawing. Application filed October 5, 1911. Serial No. 653,040. Renewed February 6, 1913. Serial To all whom, it may concern: I

Be it known that'I, JAcoB S. RoBnsoN, a citizen'of the. United States, residing at Au Sable Forks, in the county of Essex and State of New York, have invented certain new and useful Improvements in Plastics and Plastic Compositions and Processes of Making Same, of which the following is a specification.

This invention relates to plastics and plastic compositions and process of making I same; and it comprises a composition of matter comprising a mlxture of sulfite Waste commingled with material united thereby sulfites, such as bisulfites of calcium or a liquor, best in concentrated undecomposed form, and a plastic argillaceous material'o-f substantially neutral character, such as kaolin or any plastic clay, in finely divided condition, the mixture being advantageously in such proportions as to" produce a pulpy' mass, the said mixture being either alone or as in a shaped article and it also comprises processes of making such composition; all

.as more fully hereinafter set forth and as claimed.

Sulfite waste liquor 1s a waste product obta ned in large quantities from the manufacture of paper pulp by theso-called sulfite process in which wood or the like 18 heated in a digester with a solution containing bimixture of the bisulfitesfof calcium and magnesium, with more or less free sulfurot s acid until the soluble or non-cellulosic constituents of'the wood, usually included under the broad term lignones are dissolved from the wood, leaving substantially pure Cellulose as a, residue. The character of the soluble compounds formed by the interaction ofthe lignones and the sulfites of the solvent during the digestion has not been fully determined, but the compounds are commonly considered to be in the nature of lignosulfonates of the bases employed and are ordinarily so called for convenience of terminology.

The sulfite wasteiliquor as it comes from the 'digesters is a rather dilute solution of the lignosulfonates and its specific gravity is low. It is also slightly acid in reaction.

. Attempts have been made to utilize the liquor in this form as an adhesive, for example. as a binder in making sand "cores for foundry purposes, fuel briquets, etc. But the dilute, untreated liquor h s been found to possess rather a low val e as a'b'inder by tration is not fully understood .Apparently the change is physical rather than chemical; at least there seems to be no decomposition of the organic compounds originally present, though there may possiblyoccur something in the nature of a polymerization, but there is a decided increase in the cementing value; the contained matters are much better binders. The concentrated liquor possesses positive adhesive properties. This may be due in part to a colloiding efiectproduced by the neutralization and subsequent treatment ofthe raw liquor. nation is true is evidenced by the fact that the concentrated product still retains its distinctive adhesive properties even when. rediluted to the density of the raw liquor. v

I have discovered that the colloid properties and adhesive and binding powers of concentrated sulfite waste liquor can be greatly increased by mixing or pulping therewith plastic clay, kaolin, or other simi lar argillaceous material in very finelydivided' condition. Clay, kaolin and similar plastic argillaceous materials are substantially neutralor indifferent materials and the chemical or physical actions involved in this heightening of the binding power do not seem to depend in any way onthe presence of highly reactive acid or basic bodies. itself has some effect as-a binder, but the binding power of the combination of clay and concentrated liquor is far greater-than the sum of their individual binding powers.

In other words, the increase in the adhesive effect is not merely additive. For example, a test briquet made up of sand to which had been added certain percentages of concenbaked at the proper temperature, showed a tensile strength of 26 pounds. A similar briqut-containing the same percentage of the liquor as before, but -no clay, tested 5% That some such explatrated liquor and clay and which had been pounds. A third similar briquetmade up with the same percentage of clay as in the first briquet, but containing no sulfite liquor, had a tensile strength of 1 pound. If the eflect of mixing the clay and liquor .were simply additive, then the first briquet should have shown not much more than 6% pounds tensile strength; while as a matter of fact it the whole mass of inert material composing unmixed materials.

the core or other molded article, without separation or localization. This effect may be due to a mutual colloiding action between the clay and the glutin. Tannin is known to have a colloiding action on clay; and it is probable that concentrated sulfite liquor, which although it may not contain true tannin has a tanning action, has. a similar influence. As before noted, the liquor itself may vbe assumed to be somewhat colloidal in character, and. this characteristic very likely be-v comes very much more pronounced in the presence of clay. Whatever may be the real explanation of the phenomenon, the fact remains that the addition of clay to sulfite liquor gives a binder having a strength farin excess of that which could be predicted from the binding powers of the separate or While concentrated sulfite liquor is best suited for preparing the adhesive composition of the present invention, I find that the addition of clay to the unconcentrated liquor, especially if the latter has been neutralized or. made slightly'basic as by treatment'with lime or other suitable neutralizing agent, confers decided adhesive and binding properties on the dilute liquor. The

product thus obtained is not ordinarily as desirable as that first described, though it is useful for some purposes. In adding lime no excess over the amount necessary to neutralize or render slightly basic should be employed since such an excess precipitates out the sulfite liquor constituents.

In preparing a composition suitable for use as a binder for sand cores in foundry work, a mixture of equal volumes of concentrated liquor and kaolin or clay, thoroughly 1 commingled and incorporated with suflicient water to yield a fluent mixture, yields a paste or pulp'which remains homogeneous even after long standing, substantially no separation of the constituents occurring. This lack of separation is probably due to the mutual reaction of the components.

This paste maybe diluted as desired and mixed with the core'sand in varying proportions according to the strength of core required. Other proportions of clay and liquor, are of course permissible; in fact there appears to be hardly any'limitto the possible range of mixtures which can be made to give a strong binder. But for said cores and like purposes, equal proportions of Waste sulfite liquor and clay, diluted with water to the desired extent, give advantaeous results. For core compounds however it is not desirable to use too much clay; an excess is apt to cause difficulty in casting operations. Very small quantities of clay have a marked effect and produce disproportionate increase in binding strength. Thus in one test it was found that a sand core containing one-fourth of one per cent. of

clay and about two per cent. of'concentrated liquor was approximately two and two-.

thirds time as strong as a core containing two per cent. of liquor and no clay. This increase in strength is out of all proportion to the amount of clay used, since the strength which that amount of clay alonewould lend, considered apart from the concentrated liquor, is hardly noticeable.

While the composition of matter herein described is -particularly advantageous for the manufacture of cores for foundry purposes, itis also highly useful in otherconnections. Where it is to be employed as a binder for fuel briquets, it is obviously best not to use too large a proportion of clay since the clay increases the amou of ash of the briquet more than does sulfi e liquor.

Mixtures of clay and sulfite liquor such as are herein disclosed are alsousefu'l in themanufacture of certain grades of paper, strawboard, and the like. Thus, a pulp or paste of concentrated liquor and kaolin or clay (which may be white or 'colored,) may be added to the paper stock in the heater to give any degree of loading desired. The colloidalv properties of the composition are peculiarly effective in securing complete and uniform, distribution of the clay loading through the body of thepaper fiber, while 'i the adhesive qualities developed from the clay" and liquor give strength and toughness to the finished paper. Asconcentrated. sul-- "fite liquor is dark in color, it should of course be decolorized before use where its natural coloring effect is undesirable, For many gradesof paper manufactures however this tinting is unobjectionable. Pearl hardening or calcium. sulfate may be used with the sulfite liquor either "in place of or in conjunction with the clay; but lay owing to its special action, gives much the bestfresults.

The material of the presentinvention is capable of use'broadly in the plastics art. Paper-pulp, asbestos, and similar fillers may be incorporated with the mixture of concen-' trated sulfite liquor and a plastic clay, and the resulting composition molded into useful articles of any desired shape. Or, the paper pulp or asbestos may be incorporated in the pulp-like mixture of argillaceous material and liquor to form a commercial binder or article, Fibrous materials such as these are desirable in the composite binder when used for some purposes. By molding into blocks and permitting the molded material to set under proper conditions, an artificial stone is produced which is suitable for certain purposes. Such artificial stone may be waterproofed if necessary in any convenient way, as by silicating'its surface or coating with tarry compositions etc.

Cementitious materials may also be added to any of the foregoing composition where deemed advisable.

By replacing the lime in the concentrated sulfite liquor by alumina, a liquor'containing soluble compounds of alumina with the organic constituents of the liquor is 1 obtained which has even higher colloiding power than the concentrated liquor contain ing the original lignosulfon-ates. Such a product may be prepared by treating waste sulfite liquor with a solution of aluminum sulfate in amount equivalent to the lime present and removing the calcium sulfate produced. For some purposes it is advantageous to use this derived product in the mixtures above described. It is somewhat more expensive however than sulfite liquor land cement.

which has been simply neutralized and concentrated, and as a rule the latter gives sufliciently good results.

As stated, further proportions of clay can be mixed with the described mixture of clay and concentrated sulfite liquor without detracting from its adhesive power and indeed with advantage. And the mixture is not unfavorably changed by contact with clay or loam, therein differing materially from ordinary cement; and it may therefore be used as a binder in plastic block and wall making with-sands and gr'avels which are too clayey, loamy or dirty for use with Port- It may indeed be used for structural purposes as a cementing binder for many clayey and earthy materials, producing walls or blocks of considerable strength. These walls orrblocks may if necessary be waterproofed or painted. -It is an excellent binder for dirt roads, producing a cement-like texture; and it is particularly useful with roads, blocks or walls carrying feldspathic rocks as it tends t produce hydrolytic changes w th production ofbinding substances. This 1s partlcularly true with mixtures containing both feldspathic rocks and calcareous materials.

What I claim is I 1. As a new'plastic material, a mixture comprising sulfite liquorand a plastic clayey material of substantially neutral character pulped together. i 2. As a new plastic' material, a mixture comprising concentrated sulfite liquor and plastic clayey material of substantially neutral character pulped together.

3. As a new plastic material, a mixture comprising neutralized sulfite liquor and plastic clayey material of substantially neutral character pulped together.

4. As a new plastic material, a mixture comprising neutralized and concentrated sulfite liquor and plastic clayey material of substantially neutral character pulped together.

5.. As a new plastic material 'a mixture comprisingsulfite liquor and plastic clayey material of substantially neutral character pulped together and bodies of inert finely divided material bound together by said liquor and clayey material.

' 6. As a new plastic material, a mixture comprising substantially equal proportions of concentrated sulfite liquor and a plastic clay pulped together. V

7. As a new plastic material,-a mixture comprising{substantially equal proportions of concentrated sulfite liquor and a plastic clay pulped together and mixed with a filler. I i

' 8. As a new plastic material, a mixture comprising the organic matter of sulfite liquor and plastic clayey material of substantially neutral character in an intimately c'ommingled condition.

9. As a new plastic material, a'mixture "comprising the organic matter of concentrated sulfite liquor and plastic clayey material' of substantially neutral character in an intimately commingled condition.

10. The process of producing hard concrete like masses which comprises treating calcareous materials with a mixture comprising the organic matters of sulfite liquor and plastic argillaceous material of substantially neutral character. 11. As a new plastic material, a composition comprising organic matters derived from sulfite liquor, plastic argillaceous mamaterial of substantially neutral character.

ture in the presence of two subscribing witnesses.

JACOB ROBESON. Witnesses: I

L. (3.. Bones,

J As. A. SHIRRAS.

' In testimony whereof, Ija'fiix my s'ignaarmixtur'e containing feldspathic rocks and terial, feldspathic material and calcareous 

